6, 10, 12-trimethyl-5, 9-tridecadien-2-one



Unit d ta s tent-" Cc t... 52192112 pound. Although this compound is not claimed herein,- the preparation thereof is described below:

2,870,210 I 6,10,12-TRIMETHYL-5,9-TRIDECADIEN-2-0NE X F K Jose 11 Donald Surmatis Pom ton Plains N. J. assi nor' to Hoifmann-La Roclie inc Nutley, J., a corp orw grams of 35'd1methyllhexen'3'ol was j i fi of New Jersey with 1500 cc. of concentrated aqueous hydrochloric acid (37% by Weight HCl concentration) at room tempera- N0 ppllcamn December 7,1954 ture for 30 minutes. The oillayer was separated, washed Sena! 473,725 twice, each time with 500 cc. of water, and dried over 1 Claim (CL 5 5 calcium chloride. The product obtained, 1-chloro-3,5-dim'ethyl-Z-hexene, had n =1.448.

p In a five-liter flask there was placed three liters of ben- This invention relates to novel chemical compounds Zane 429 of ethyl acetoacetate and 162 of sodmm and to processes for their preparation. More particularmethylate' 428 the Pmduct of the Preceding P ly, it relates to the novel compound 6,10,12-trimethyl-5,9- h 1- i was fidded at Q z and to novel processes and novel C. Within 30 minutes, and stirring was continued for SIX chemical intermediates having utility to prepare this com 119mg at 6,O 70 The leactl'on mixture a w pound. '6,10,12-trimethyl-5,9-tridecadien-2-one is usewlth two of water and the was-hstlugd ofi ful in the perfume, cosmetic, flavoring and pharmaceuti- P a Vacuum of 100 to yield Y- cal industries, e. g. as an odor-imparting agent in the dlmethyl-simnen-z-qne straw'colored preparation of perfumes and of scented compositions The emlre quantity Y generally, and as a flavor constituent of flavoring composinonen'z'one Producec! above was dlssolved In ZhteYS of dons. h ,l ethyl alcohol To thls was added 200 g. of solid potas- One comprehensive embodiment of the invention s ium hydroxide and 200 cc. of Water. The mixture was lates to a process of making 6,10,12-trimethyl-5,9-trisllrred for 4 hours at 40400 To the resulting decadi'en-2-one which comprises the steps of halogenating of the Potassmm salt of 'c ii 3,7,9 trimethy1 L6 decadien 3 ol to produce 1 ha1o 37,9 nonen-Z-one was then added concentrated aqueous hydrotrimethyl-2,6-decadiene, reacting the latter with a lower chlonc (37% welght HCD Q a seraratqry alkyl acetoacetate to produce 3-lower carbalkoxy-6,l0,12- funnel solution was 9F8 3 acld- Thllfty trimethyl-S,9-tridecadien-2-one and subjecting the latter Utes w requlrefilfm the addltlofl- The solution was to ketonic scission to produce 6,l0,12-trimethyl-5,9-trithen surfed i hour 50 decadiemzona The reaction mixture was diluted w1th two liters of The first step in the novel synthesis of the instant inwater and the 011 layer was remowal by means of a 2 Venn-On can be effected by reacting 3,7,9 tn-methy1 1,6 ratory funnel. The aqueous portion was extracted with decadl-en 3 ol with a halogenafing agent appropriate to 500 cc. of benzene. The combined 0118 were washed neuconvert the said alcohol to a hydrohalic acid ester thereof, tralf water and i i l P e. g. phosphorus tribromide, dry hydrogen chloride, and g distilled at at the like. It is preferred to effect the halogenation by re- 40 h a Pleasant i i odor remlmscem acting 3,7,9-trimethyl-1,6-decadien-3-ol with a concenof apple Juice 24dmlthophenylhydrazPne trated aqueous solution of hydrochloric acid or hydrogg fig g gf fii The semlcarbazone denva' In 1.5 liters of liquid ammonia there was dissolved 41.4 weight 1101 concentration, or commercial concentrated of metallic sodmm' gas Was passed mm weight HBr concentration, at a temperature between about 0 C. and about room temperature. gf lsmmltes- 2 Then 3 sollutign of gramsfof 611,8-

The next step in the novel synthesis can be effected by y E 1 5 t 0 Y1 reacting the 1-halo-3,7,9-trimethyl-2,6-decadiene with a et erwas roppe m M mmu e slmng lower alkyl acetoacfitate e g ethyl acetoacetate or was continued for fifteen hours While a slow stream of methyl acetoacetate, in the presence of an alkaline conacetylene was imbued Into the reacmn mlxture' densation agent, e. g. an alkali metal such as sodium or T aIPmOma w theweupon evaporated fromfhe potassium, or an alkali metal lower alkoxide such as acuon 1 wlth the of a w stream of P- sodium methoxide or potassium ethoxide In this Step it The residue was poured into two liters of 5% sulfuric is permissible to work with a crude l-halo-3,7,9-trimethylacld' The 011 layer was removed and washed neutral 2,6-decadiene as produced by the preferred method of wateronfractwnafion, ,7,9:trimethyl-l-decyn-fioperating the first step, without special purification of the was (gnawed m a fi'actlon dlsmhng at 72 at said 1-halo-3,7,9-trimethyl-2,6-decadiene. "D

The final step of the novel synthesis comprises subjectof was f ing the 3 1 -b lk 6 lo lz i h l 5 g id with an equal volume of petroleum ether and placed n a dien-2-one produced by the second step (which compound flask wlth grams of 5% 1eadjPa11ad1Pn?"n-ca16111111 also need not be further purified) to ketonic scission. carbonate Catalyst [Lllldlah Helvetlca Chlmlca a 3 This can be accomplished, for example, by saponifying 446 This was hydrogenated at 0116 atmosphere the 3-lower carbalkoxy-fi,10,1Z-trimethyl-5,9-tridecadienga g hy og n pr s re until 0-97 mol of hydrogen was 2-one with an alkali metal hydroxide and then acidifying consumed. On fractionation of the reaction mixture, the resulting alkali metal salt of 3-carboxy-6,l0,I2-trithere was obtained 3,7,9-trimethyl-1,6-decad1en-3-ol, dismethyl-5,9-tridecadien-2-one and heating to complete the fi g at at 20 decarboxylation. The invention is further disclosed in the following ex- The starting material of the above described synthesis, amples, which are illustrative but not limitative thereof, 3,7,9-trimethyl-1,6-decadien-3-ol, is itself a novel comthe invention being limited only by the appended cla m.

Example 1 Example 2 In a two-liter flask were placed 1000 cc. of benzene,

104 g. of ethyl acetoacetate, and 40 grams of sodium methylate. After stirring for 30 minutes, 145.5 g. of the product of Example 1, 1-chloro-3,7,9-trirnethyl 2,6-decadiene, was dropped in from a separatory funnel in 30 minutes. The reaction mixture was stirred at 60 to 70 C. for four hours. After cooling to room temperature, the mixture was'washed with 100 cc. of water and the benzene was removed by distillation under vacuum. The residue remaining in the flask consisted essentially of 3- carbethoxy-6,l0,1Z-trimethyl-S,9-tridecadien-2-one.

Example 3 500 cc. of ethyl alcohol, 70 g. of potassium hydroxide, and 50 cc. of water were added to the flask containing the entire quantity of 3-carbethoxy-6,10,12-trimethyl-5,9 tridecadienZ-one produced in Example 2 above. The

saponifleation was carried out by stirring the mixture at 40 to 50 C. for four hours. The decarboxylation of the resulting potassium salt of 3-carboxy-6Ll0,l2-trimethyl- 5,9-tridecadien-2-one was accomplished by adding concentrated aqueous hydrochloric acid to the stirred mixture 4 until strongly acid. 40-50 C. for two hours.- The cooled solution was diluted with 500 cc. of water. The oil layer was separated, and the aqueous portion was extracted with 500cc. of petroleum ether. and removing the solvent, the product was fractionated in vacuo. 6,10,IZ-trirnethyl-5,9-tridecadien-2-one distilled at 107 109 C. at 0.7 mm, n =1.4652. This material has a pleasant fruity fragrance and can be used to impart a fruity note to floral perfume compositions. It can also be used as a constituent of synthetic fruit flavors, such as pineapple, pear and apple. In comparison to esters previously used in analogous perfume and flavoring compositions, the novel ketone above referred to is characterized by its marked stability.

I claim: 6,10,12-trimethy1-5,9-tridecadien-2-one.

References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Karrer: Organic Chemistry, 4th ed., 1950, p. 705.

Stirring was then continued at- After water washing the combined oils UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,870,210 January 20,- 1959 Joseph Donald Surmatis It is herebfir certified that error appears in the-printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, line 17, for "100 cc. of Water read 1000 cc. of Water Signed and sealed this 12th day of May 1959.

SEAL) Attest:

KARL Hu AXLINE Attesting Oflicer ROBERT C. WATSON Commissioner of Patents 

